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Issue 47, 2013
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Tautomeric effect of hydrazone Schiff bases in tetranuclear Cu(II) complexes: magnetism and catalytic activity towards mild hydrocarboxylation of alkanes

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Abstract

Three new tetranuclear copper(II) complexes [Cu(HL1)]4·4EtOH (1·4EtOH), [Cu(HL2)]4 (2) and [Cu(H2L3)]4(NO3)4·2H2O (3·2H2O) have been synthesized using three different hydrazone Schiff base ligands derived from the condensation of the aromatic acid hydrazides 2-hydroxybenzo-, 2-aminobenzo- or benzo-hydrazide, with 2,3-dihydroxybenzaldehyde. Complexes 1 and 3 have been characterized by single crystal X-ray diffraction analysis. The coordinating behaviour of the ligand depends on the nature of the ortho substituent present in the hydrazide moiety. The ligands bearing a strong electron donating group (by resonance) in the ortho position undergo complexation via enolization and deprotonation, whereas the absence of such an effect leads to complexation via the keto form, and two different types of tetranuclear Cu(II) clusters, viz. open-cubane and cubane, are obtained. Variable temperature magnetic susceptibility measurements of complexes 1 and 3 have been carried out to examine the nature of magnetic interaction between the Cu(II) centres. All the three complexes (1–3) act as good catalyst precursors towards mild hydrocarboxylation of linear and cyclic alkanes into carboxylic acids in water–acetonitrile medium.

Graphical abstract: Tautomeric effect of hydrazone Schiff bases in tetranuclear Cu(ii) complexes: magnetism and catalytic activity towards mild hydrocarboxylation of alkanes

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Publication details

The article was received on 06 Sep 2013, accepted on 07 Sep 2013 and first published on 26 Sep 2013


Article type: Paper
DOI: 10.1039/C3DT52453A
Citation: Dalton Trans., 2013,42, 16578-16587
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    Tautomeric effect of hydrazone Schiff bases in tetranuclear Cu(II) complexes: magnetism and catalytic activity towards mild hydrocarboxylation of alkanes

    M. Sutradhar, M. V. Kirillova, M. F. C. Guedes da Silva, C. Liu and A. J. L. Pombeiro, Dalton Trans., 2013, 42, 16578
    DOI: 10.1039/C3DT52453A

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